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The MONITOOL project (2017-2023) was carried out to describe the relationships between total dissolved and labile metal concentrations measured in spot water samples and in concurrently deployed Diffusive Gradients in Thin-films (DGTs) passive samplers, respectively. The ultimate aim was to adapt existing marine metal Environmental Quality Standards (EQS marine water ) for DGTs, enabling their use in the context of the European Directives (the Water Framework Directive (WFD) and the Marine Strategy Framework Directive (MSFD)). Time-integrated metal concentrations provided by DGTs, representing several days, are an advantage compared to conventional spot sampling, especially in highly dynamic systems, such as transitional waters. Hence, the MONITOOL project aimed to provide a robust database of dissolved and labile metal concentrations in transitional and coastal waters, based upon co-deployments of DGTs and collection of spot water samples at several sampling sites (England, France, Ireland, Italy, Northern Ireland, Portugal, Scotland and Spain), followed subsequently by DGT and water metal analysis. Samplings were carried out in 2018 and 2022, following agreed protocols developed in the framework of the project. The MONITOOL dataset includes metal concentrations from DGTs, measured with Inductively Coupled Plasma Mass Spectrometry (ICP-MS: Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn) and in concurrently collected spot water samples by ICP-MS (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) and Anodic/Cathodic Stripping Voltammetry (ASV/CSV: Cd, Pb, Ni). Moreover, data on seawater physical-chemical parameters (salinity, temperature, dissolved oxygen, pH, turbidity, total suspended solids, dissolved organic carbon, and total organic carbon) is provided. This database presents the results obtained using, concurrently, different forms of sampling and analytical techniques, enabling the comparison of the results obtained by these strategies and allowing the adaptation of EQS in marine water (EQS marine water) to DGTs (EQS DGT ), in the context of the WFD. Moreover, due to the large number of sampling sites, it could also be used for other types of research, such as those dealing with metal speciation or the determination of baseline levels., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

The accumulation of contaminants in aquatic organisms is of concern to human health due to the potential for exposure through the consumption of seafood. This dataset presents the levels of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and 12 dioxin-like polychlorinated biphenyls (DL-PCBs) (PCB-81, PCB-77, PCB-126, PCB-169, PCB-123, PCB-118, PCB-114, PCB-105, PCB-167, PCB-156, PCB-157 and PCB-189) in bivalves collected annually between 2008 and 2023 from the four Shellfish Production Areas of the Basque coast (southeastern Bay of Biscay). Additionally, data on 6 non-dioxin like polychlorinated biphenyls (NDL-PCBs) (PCB-28, PCB-52, PCB-101, PCB-153, PCB-138 and PCB-180) is provided for the 2012-2023 time period. Depending on the availability of bivalves at each Shellfish Production Area, different species, such as mussels ( Mytilus galloprovincialis ) and oysters ( Magallana gigas and Ostrea edulis ) were used for the evaluation. Bivalve samples were analyzed at the accredited Laboratory of Dioxins of the Institute of Environmental Assessment and Water Research - CSIC in Spain, following standardized methodologies according to the specific requirements established at the corresponding EU Regulation. Concentrations and the World Health Organization-Toxic Equivalents (WHO-TEQ) were calculated. Considering the data from the four Shellfish Production Areas and the study period, WHO-TEQ values ranged from 0.12 to 0.64 pg g -1 wet weight for PCDD/Fs and from 0.45 to 2.23 pg g -1 wet weight for DL-PCBs, whereas concentrations ranged from 7.45 to 51.10 ng g -1 wet weight for NDL-PCBs. This database is useful for (i) assessing the spatial and temporal trends of PCDD/Fs and various PCBs in bivalves from the Basque coast, (ii) determining the relative contribution of different congeners, (iii) comparison with levels for human consumption and environmental quality standards, as well as with levels of other biogeographical areas, and (iv) the management of Shellfish Production Areas on the Basque coast., (© 2023 The Authors. Published by Elsevier Inc.)

European Commission has approached the challenge of End-Of-Life (EOL) fishing gear and Abandoned, Lost, or otherwise Discarded Fishing Gear (ALDFG) by focusing on circular economy. Current directives highlight the need to provide a proper management to EOL fishing gears, fostering their separate collection, transport, and treatment from a circular perspective. They also request Member States to set collection and treatment targets. However, this is far from being widely implemented in a coordinated manner. In the quest to explore the Spanish case, this contribution aims at providing insights on the amount and type of EOL fishing gear and management practices carried out in different Spanish ports, as well as recycling options for such gears. Data was collected through an online survey, interviews to stakeholders, and visits to ports. Composition, degradation and mechanical recyclability of EOL samples were assessed. Yearly, 1643 tonnes of EOL fishing gear (mainly nets) are discarded in Spanish ports from trawling (97.5%), gillnet/trammel nets (2.3%) and purse seine (0.2%) fisheries. High-density polyethylene (from trawling nets) is the most common discarded polymer, followed by polyamide 6 (from gillnets/trammel net and purse seine nets). EOL fishing gear management is diverse in Spain as it depends on the nature of the port (who governs it, either regional or national govern), special agreements between local fishers' guilds and waste managing companies, the waste managers in port, etc. Polyamide nets are degraded but in good condition to be recycled mechanically; for trawl nets chemical recycling is more suited due to their degraded state. Currently, few recycling companies exists in Spain that are engaged on mechanical recycling of EOL fishing gears, none in chemical recycling. Therefore, a more comprehensive analysis, coordination, and smart logistics are needed to make the collection and recycling of EOL fishing gear possible., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

In order to move forward in the acceptance of a novel contaminant monitoring technique (Diffusive Gradients in Thin-films: DGT) for assessment of marine water bodies, sensu the WFD, an Inter-Laboratories Comparison (ILC) exercise (nine Europeans laboratories) was organized in the framework of the Interreg Atlantic Area MONITOOL project, which focused on the use of the DGT technique for the measurement of WFD priority metals (Cd, Ni and Pb). Reproducible results were obtained for each metal by several laboratories, supporting the assertion that DGT analysis can be performed satisfactorily by laboratories experienced in measuring metals at trace levels in marine environments, even if they have limited practice in DGT analysis. According to the Z-score analysis, among the 9 participating laboratories, 3 had 100 % of satisfactory results for Cd, Ni, and Pb, 3 had >80 % satisfactory results and 2 had about 60 % satisfactory results. This work highlights the need to clearly describe the DGT method in order to control sources of contamination during analytical steps, in particular the resin gel retrieval and the elution steps. Such international intercomparison exercise is an important step to develop the laboratory network involved in DGT analysis and contributes to the improvement of data quality., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

The study of the presence of antibiotics in the aquatic environment is a preliminary step to analyse their possible harmful effects on aquatic ecosystems. In order to monitor their occurrence in the aquatic environment, the European Commission established in 2015, 2018, and 2020 three Watch Lists of substances for Union-wide monitoring (Decisions (EU) 2015/495, 2018/840, and 2020/1161), where some antibiotics within the classes of macrolides, fluoroquinolones and penicillins were included. In the Basque coast, northern Spain, three macrolide antibiotics (erythromycin, clarithromycin, azithromycin) and ciprofloxacin were monitored quarterly from 2017 to 2020 (covering a period before and after the COVID19 outbreak), in water samples collected from two Waste Water Treatment Plants (WWTPs), and three control points associated with receiving waters (transitional and coastal water bodies). This work was undertaken for the Basque Water Agency (URA). The three macrolide antibiotics in water showed a frequency of quantification >65 % in the Basque coast, with higher concentrations in the WWTP emission stations than in receiving waters. Their frequency of quantification decreased from 2017 to 2020, as did the consumption of antibiotics in Spanish primary care since 2015. Ciprofloxacin showed higher frequencies of quantification in receiving waters than in wastewaters, but the highest concentrations were observed in the WWTP emission stations. Although consumption of fluoroquinolones (among which is ciprofloxacin) in primary care in the Basque Country has decreased in recent years, this trend was not observed in the waters sampled in the present study. On the other hand, concentrations of clarithromycin, azithromycin, and ciprofloxacin in receiving waters exceeded their respective Predicted No-Effect Concentrations, so they could pose an environmental risk. These substances are widely used in human and animal medicine, so, although only ciprofloxacin is included in the third Watch List, it would be advisable to continue monitoring macrolides in the Basque coast as well., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Numerical models point to the south-east Bay of Biscay as a convergence area for floating particles, including plastics. The few existing studies on plastic abundance in the area mainly focus on open waters and yet information on the coastal area is limited. To fill this gap, neustonic samples were taken along the coastal waters of the south-east Bay of Biscay (2017-2020) to define the spatial distribution of plastic abundances and composition. Results show an average plastic abundance of 739,395 ± 2,625,271 items/km 2 (998 ± 4338 g/km 2 ). French waters were more affected, with five times higher plastic abundances than Spanish coasts. Microplastics represented 93 % of the total abundance of plastic items (28 % in weight), mesoplastics 7 % (26 %) and macroplastics 1 % (46 %). This study demonstrates that this area is a hotspot for plastic with levels in coastal waters similar to those in the Mediterranean Sea or other litter aggregation areas., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study investigates the relationships among Ni, Cd and Pb's different chemical forms determined by different methodologies in coastal and transitional waters across a broad geographical scale. Concentrations were measured in spot samples and through passive sampling (DGT). High variability of metal concentrations was found among sampling sites and methodologies due to natural water fluctuations rather than to a given metal or method. Total dissolved metal concentrations in spot samples were lower than the EQS-WFD values. The labile fractions of Cd and Pb, measured in spot samples by Anodic Stripping Voltammetry and by DGT-ICPMS, were highly correlated. Similar labilities were found for Cd, while for Pb, the ASV labile fraction was ≈50% lower. These results reflect the pool of mobile and labile species available towards each technique kinetic window, and they seem not to be affected by discrete sampling flaws., (Crown Copyright © 2022. Published by Elsevier Ltd. All rights reserved.)

The current study evaluates the effect of seawater physico-chemical characteristics on the relationship between the concentration of metals measured by Diffusive Gradients in Thin films (DGT) passive samplers (i.e., DGT-labile concentration) and the concentrations measured in discrete water samples. Accordingly, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to measure the total dissolved metal concentrations in the discrete water samples and the labile metal concentrations obtained by DGT samplers; additionally, lead and cadmium conditional labile fractions were determined by Anodic Stripping Voltammetry (ASV) and total dissolved nickel was measured by Cathodic Stripping Voltammetry (CSV). It can be concluded that, in general, the median ratios of DGT/ICP and DGT/ASV(CSV) were lower than 1, except for Ni (median ratio close to 1) and Zn (higher than 1). This indicates the importance of speciation and time-integrated concentrations measured using passive sampling techniques, which is in line with the WFD suggestions for improving the chemical assessment of waterbodies. It is the variability in metal content in waters rather than environmental conditions to which the variability of the ratios can be attributed. The ratios were not significantly affected by the temperature, salinity, pH, oxygen, DOC or SPM, giving a great confidence for all the techniques used. Within a regulatory context such as the EU Water Framework Directive this is a great advantage, since the simplicity of not needing to use corrections to minimize the effects of environmental variables could help in implementing DGTs within monitoring networks., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

This protocol was developed based on the knowledge acquired in the framework of the Interreg MONITOOL project (EAPA_565/2016) where extensive sampling campaigns were performed in transitional and coastal waters covering eight European countries. It provides detailed procedures and guidelines for the sampling of these waterbodies by concurrent collection of discrete water samples and the deployment of Diffusive Gradient in Thin-films (DGT) passive samplers for the measurement of trace metal concentrations. In order to facilitate the application of this protocol by end-users, it presents steps to follow in the laboratory prior to sampling campaigns, explains the procedures for field campaigns (including in situ measurement of supporting parameters) and subsequent sample processing in the laboratory in preparation for trace metal analyze by inductively coupled plasma-mass spectrometry (ICP-MS) and voltammetry. The protocol provides a systematic, coherent field sampling and sample preparation strategy that was developed in order to ensure comparability and reproducibility of the data obtained from each project Partner in different regions. • Standardization of the concurrent sampling of transitional and coastal waters by DGT passive samplers and spot sampling. • Robust procedures and tips based on existing international standards and comprehensive practical experience. • Links to demonstration videos produced within the MONITOOL project., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2021 Published by Elsevier B.V.)

The study of the presence in the aquatic environment of certain substances considered as contaminants of emerging concern (CEC) is a preliminary step to the analysis of the possible harmful effects on aquatic ecosystems and the establishment of the corresponding environmental quality standards. In order to monitor the occurrence of CECs in the aquatic environment, the European Commission established in 2015 and 2018 two watch-list of substances for Union-wide monitoring in the field of water policy (Decision (EU) 2015/495 and Decision (EU) 2018/840). In the coast of the Basque Country, southeast of the Bay of Biscay, 19 of these watch list substances were monitored quarterly from May 2017 to March 2019. Water samples were collected at the effluent of three wastewater treatment plants and five control points associated with receiving waters (transitional and coastal water bodies). The most frequently quantified substances were azithromycin (91%), imidacloprid (82%), clarithromycin (80%), diclofenac (78%) and erythromycin (73%), with frequencies of quantification higher in wastewaters (83-100%) than in receiving waters (70-85%). In general, concentrations in wastewater were also higher than in receiving waters, indicating a dilution effect in the environment. In receiving waters, six out of the nineteen substances monitored exceeded their respective Predicted No-Effect Concentrations: azithromycin (34%), imidacloprid (9%), 17β-estradiol (E2) (9%), clarithromycin (7%), ciprofloxacin (7%), and diclofenac (5%); and therefore, their levels could pose an environmental risk., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Introduction: The aim of our study is to describe the types of dementia found in a series of patients and to estimate the level of agreement between the clinical diagnosis and post-mortem diagnosis., Material and Methods: We conducted a descriptive analysis of the prevalence of the types of dementia found in our series and we established the level of concordance between the clinical and the post-mortem diagnoses. The diagnosis was made based on current diagnostic criteria., Results: 114 cases were included. The most common clinical diagnoses both at a clinical and autopsy level were Alzheimer disease and mixed dementia but the prevalence was quite different. While at a clinical level, prevalence was 39% for Alzheimer disease and 18% for mixed dementia, in the autopsy level, prevalence was 22% and 34%, respectively. The agreement between the clinical and the autopsy diagnoses was 62% (95% CI 53-72%)., Conclusions: Almost a third of our patients were not correctly diagnosed in vivo. The most common mistake was the underdiagnosis of cerebrovascular pathology., (Copyright © 2016 Sociedad Española de Neurología. Publicado por Elsevier España, S.L.U. All rights reserved.)

Background: The Alliance Breast Cancer (ABC) program is a community-based initiative developed and implemented to address the needs of Hispanic women faced with a cancer diagnosis or cancer survivorship issues., Objectives: This article evaluates the effectiveness of a community effort to address breast cancer-related disparities among Hispanic women., Methods: Nurse scientists collaborated with program staff to conduct a systematic five-year program evaluation. Data sources included monthly and annual reports, participant tracking databases, and an annual satisfaction survey., Findings: Hispanic breast cancer survivors who participated in the program expressed feeling very satisfied with the services and believe that it addresses the specific barriers faced by this population. The ABC program serves as a best practice example to other communities forging partnerships to address health disparities and community needs in a culturally tailored manner.

Using a long-term (1995-2014) monitoring network, from 51 sampling stations in estuaries and coasts of the Basque Country (Bay of Biscay), the objective of this investigation was to assess the responsiveness of 83 variables in water (18), sediments (27), biota (26), phytoplankton (2), macroinvertebrates (5) and fishes (5) to different human pressures and management actions. We used a total of 3247 series of data to analyse trends of improvement and worsening in quality. In a high percentage of the cases, the management actions taken have resulted in positive effects in the environment, as shown by the trend analysis in this investigation. Overall, much more trends of improvement than of worsening have been observed; this is true for almost all the media and biological components studied, with the exception of phytoplankton; and it applies as well to almost all the stations and water bodies, with the exception of those corresponding to areas with water treatment pending of accomplishment. In estuaries with decreasing human pressures during the period, the percentage of series showing quality improvement was higher (approx. 30%) than those showing worsening of quality (12%). Moreover, in those water bodies showing an increase of pressure, variables which can be considered indicators of anthropogenic effects showed negative trends (quality worsening). On the other hand, some of the variables analysed were more affected by natural variability than by changes in pressures. That was the case of silicate, nitrate and suspended solids, which followed trends correlated to salinity, which, in turn, was related to the rainfall regime during the study period., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Sole and hake, together with sediments, were collected during two campaigns along the Basque continental shelf to study the utility of two existing histopathological indices for assessing the biological effects of contaminants to implement the European Marine Strategy Framework Directive. Hepatic and gonadal histopathology were measured, and metal and/or organic contaminants were determined in both liver and sediments. Sediments from the Basque continental shelf were found to be moderately impacted by metals but non-impacted by organic compounds. Metal bioaccumulation and histopathological lesions in liver were higher in sole than in hake, although non-specific and early non-neoplastic toxicopathic lesions were observed in both species. No gross alterations were recorded in gonad. The two histopathological indices applied were highly correlated in both organs but the lack of correlation between sediment contamination levels, bioaccumulation and histopathological indices suggests that other factors, rather than pollution alone, are responsible for the biological effects observed., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Bivalve histopathology has become an important tool in aquatic toxicology, having been implemented in many biomonitoring programmes worldwide. However, there are various gaps in the knowledge of many sentinel organisms and the interference of confounding factors. This work aimed (i) to develop a detailed semi-quantitative histopathological index of the digestive gland and gonad of the Mytilus galloprovincialis mussel collected from five sites contaminated with distinct patterns of organic and inorganic toxicants along the Basque coast (SE Bay of Biscay) and (ii) to investigate whether seasonal variability and parasitosis act as confounding factors. A total of twenty-three histopathological alterations were analysed in the digestive gland and gonad following a weighed condition index approach. The alterations were integrated into a single value for a better understanding of the mussels' health status. The digestive gland was consistently more damaged than the gonad. Mussels from the most impacted sites endured the most significant deleterious effects showing inflammation-related alterations together with digestive tubule atrophy and necrosis. Neoplastic diseases were scarce, with only a few cases of fibromas (benign neoplasia). In contrast, in moderately or little impacted sites, contamination levels did not cause significant tissue damage. However, parasites contributed to overestimating the values of histopathological indices (i.e. more severe tissue damage) in mussels from little impacted sites, whilst the opposite occurred in mussels from highly polluted sites. Accordingly, inter-site differences were more pronounced in autumn when natural physiological responses of advanced maturation stages did not interfere in the histological response. In conclusion, although seasonal variability and parasitosis mask the response of histopathological indices, this biomonitoring approach may provide good sensitivity for assessing the health status of mussels if fluctuations of these confounding factors are considered., (Copyright © 2015 Elsevier B.V. All rights reserved.)

According to Water Framework Directive requirements, Member States must identify and analyze effects derived from human pressures in aquatic systems. As different kind of pressures can impact water bodies at different scales, analyses of spatio-temporal evolution of water bodies becomes essential in order to understand ecosystem responses. In this investigation, an analysis of spatio-temporal evolution of sedimentary metal pollution (Cd, Cr, Cu, Hg, Ni, Pb, Zn) in 12 Basque estuaries (Bay of Biscay) is presented. Data collected in extensive sampling surveys is the basis for the GIS-based statistical approach used. The implementation of pollution abatement measures is reflected in a long-term decontamination process, mostly evident in estuaries with highest historical sediment pollution levels. Spatial evolution is determined by either naturally occurring or human driven processes. Such spatial processes are more obviously being reflected in estuaries with lower historical sediment pollution levels., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) were measured in surficial sediments at, the ports of Pasaia and Bilbao, together with other mid- and small-size harbours of the Basque Country (northern Spain), in 2007-2008. The highest values of the sum of the three measured butyltin species (3523-3640 ng g(-1), as Sn) were found at sampling stations near to shipyards located within the port of Pasaia. The highest value of TBT concentration (3143 ng g(-1), as Sn) was found at the marina of Getxo, in the port of Bilbao. The degree of TBT degradation varied greatly between sampling stations, being found to be generally higher in those sediments with higher values of redox potential and lower values of TBT concentration (normalized by organic matter content)., (Copyright 2009 Elsevier Ltd. All rights reserved.)

The European Water Framework Directive (WFD) establishes a framework for the protection and improvement of estuarine (transitional) and coastal waters, attempting to achieve good water status by 2015; this includes, within the assessment, biological and chemical elements. The European Commission has proposed a list of priority dangerous substances (including metals such as Cd, Hg, Ni and Pb), with the corresponding list of environmental quality standards (EQS), to assess chemical status, but only for waters. In this contribution, a long-term (1995-2007) dataset of transitional and coastal water and sediment trace elements concentrations, from the Basque Country (northern Spain), has been used to investigate the response of these systems to water treatment programmes. Moreover, the approach proposed in the WFD, for assessing water chemical status (the 'one out, all out' approach), is compared with the integration of water and sediment data, into a unique assessment. For this exercise, background levels are used as reference conditions, identifying the boundary between high and good chemical status. EQS are used as the boundary between good and moderate chemical status. This contribution reveals that the first approach can lead to misclassification, with the second approach representing the pattern shown by the long-term data trends. Finally, the management implications, using each approach are discussed.

The European Water Framework and Marine Strategy Directives relate to the assessment of ecological quality, within estuarine and coastal systems. This legislation requires quality to be defined in an integrative way, using several biological elements (phytoplankton, benthos, algae, phanerogams, and fishes), together with physico-chemical elements (including pollutants). This contribution describes a methodology that integrates all of this information into a unique quality assessment for 51 stations from 18 water bodies, within the Basque Country. These water bodies are distributed into four typologies, including soft-bottom coastal areas and three types of estuaries. For each station, decision trees were used to integrate (i) water, sediment and biomonitor chemical data to achieve an integrated physico-chemical assessment and (ii) multiple biological ecosystem elements into an integrated biological assessment. Depending on the availability of ecological quality ratios or global quality values, different integration schemes were used to combine station assessments into water body assessments on a single scale. Several examples from each element have been selected, to illustrate their responses to different pressures; likewise, to establish how the assessed integrated quality has changed, over time. The results made biological and ecological sense and physico-chemical improvements were often correlated with improvements in the quality of benthos and fishes. These tools permit policy makers and managers to take decisions, based upon scientific knowledge, in water management, regarding the mitigation of human pressures and associated recovery processes.

Odorous organic compounds from liquid and gas samples of animal wastes were studied by headspace (HS)-solid-phase microextraction (SPME)-GC-MS. 1-Pirenyldiazomethane (PDAM) was adsorbed/absorbed on the SPME fibre in order to obtain the corresponding ester derivatives during the preconcentration step. The SPME fibre was immersed into a PDAM solution. Then, the SPME fibre was withdrawn and exposed to the HS of the liquid cow slurry. This way derivatisation of VFAs took place in the SPME fibre together with the preconcentration of the rest of the analytes of interest. The analytes were desorbed in the hot injection port (300 degrees C) of a GC-MS for 3 min. Four different fibre types and different immersion periods of the fibre in the PDAM solution were studied in order to obtain the best sensitivity with the selected fibre. Accuracy, precision and the LODs were calculated using spiked liquid and gas samples. The possibility of storing liquid samples after sampling by preconcentration on the fibre was also considered. Storage time and temperature were studied. The optimised method was applied to the determination of the analytes in liquid and gas samples from cow slurries from an intensive production farm.

Inorganic mercury and methylmercury are determined in natural waters by injecting the filtered samples onto a low cost commercial flow injection system in which an anion exchange microcolumn is inserted after the injection loop (FIA-IE). If hydrochloric acid is used as the carrier solution, the HgCl4(2-) species (inorganic mercury) will be retained by the anion exchanger while the CH3HgCI species (methylmercury) will flow through the resin with negligible retention. Four anion exchangers and seven elution agents were checked, in a batch mode, to search for the best conditions for optimal separation and elution of both species. Dowex M-41 and L-cysteine were finally selected. Mercury detection was performed by cold vapour-electrothermal atomic adsorption spectrometry (HG-ETAAS). Both systems were coupled to perform the continuous on-line separation/detection of both inorganic mercury and methylmercury species. Separation and detection conditions were optimized by two chemometric approaches: full factorial design and central composite design. A limit of detection of 0.4 microg L(-1) was obtained for both mercury species (RSD < 3.0% for 20 microg L(-1) inorganic and methylmercury solutions). The method was applied to mercury speciation in natural waters of the Nerbioi-lbaizabal estuary (Bilbao, North of Spain) and recoveries of more than 95% were obtained.